CN104925855B - Preparation method of TiCxOy - Google Patents

Abstract

The invention relates to a preparation method of TiCxOy, belongs to the field of preparation of inorganic nonmetallic materials and solves the technical problem of providing a method for preparing uniform TiCxOy by adopting vapor deposition. The preparation method comprises the following steps: A, controlling the temperature of a reaction system to be 400-800 DEG C to enable gaseous TiCl4 to be in fully contact and react with CO and H2; B, collecting a solid matter obtained by formation of solid deposition, and the solid matter is TiCxOy (x plus y equals 1). The TiCxOy prepared by adopting the preparation method which is provided by the invention is good in uniformity compared to that prepared by adopting a carbothermic method, and as the gas-phase reaction is carried out during the preparation process, the formed nucleuses can hardly form large-grain matters, therefore the product is extremely fine and uniform, beneficial for subsequent processing and making, and suitable for being used as raw materials for powder metallurgy and soluble anode electrolysis.

Description

A kind of preparation method of carbon oxygen titanium

Technical field

The present invention relates to a kind of preparation method of carbon oxygen titanium, belong to Inorganic Non-metallic Materials preparation field.

Background technology

Carbon oxygen titanium (tic_xo_y, wherein x+y=1) and it is in carbon thermal reduction tio at first₂During be found, because its have excellent Different performance, such as high-melting-point, high rigidity, good heat conductivity, electric conductivity and resistance to corrosion etc., become decoration, cutting, electrode Etc. the new material of industry, studied by the more and more worker of going together.

At present, the carbon oxygen titanium method of preparation mainly has thermal reduction, gas-solid reaction method, electrochemical deoxidising method etc. admittedly, but All there is product quality skewness phenomenon in these methods.As carbon thermal reduction tio₂The carbon oxygen titanium of preparation is because of machinery and reduction process Micro- Qu Zaocheng product uneven, have a strong impact on the physicochemical properties such as its conduction, hardness.

The present inventor on this basis, is intended to provide a kind of brand-new method to prepare uniform carbon oxygen titanium.

Content of the invention

Technical problem solved by the invention is a kind of method providing employing vapour deposition to prepare uniform carbon oxygen titanium.

The preparation method of carbon oxygen titanium of the present invention comprises the following steps:

A, control temperature of reaction system at 400～800 DEG C, by gaseous ticl₄With co and h₂It is fully contacted reaction；

B, collection form deposition gained solid content with solid, and this solid content is carbon oxygen titanium.

The reaction principle of preparation method of the present invention such as formula (1):

${\mathrm{ticl}}_4+\frac{1}{2}co+2h_2={\mathrm{tic}}_{0.5}{o}_{0.5}+4hcl---\left(1\right)$

In preparation process, for ensureing efficiency and the energy efficient of reaction, therefore the temperature control of reaction system in step a is existed 400～800 DEG C.

In preparation process, for ensureing efficiency and the energy efficient of reaction, co and h₂Need excess, to ensure the complete of reaction, Therefore ticl₄、co、h₂Between be calculated in molar ratio as 1:1.2～2:2.4～4.

Due to can generate band corrosive hcl gas during reaction, therefore this reaction need to select the material of corrosion resistance, such as nickel, Carborundum, titanium nitride etc..Also have unreacted completely co and h in tail gas₂, hcl, co and h₂Belong to harmful influence, therefore after reaction terminates Tail gas need to first pass through alkali liquor absorption and process, then can discharge after carrying out lighting process.Wherein, alkali liquor optional naoh aqueous solution, koh Aqueous solution etc..Further preferably, alkali liquor mass fraction is 5-20%, preferably 10%.

For realizing technique scheme, during concrete operations, the preparation method of carbon oxygen titanium of the present invention can adopt flow reactor Or the reaction such as hermetically sealed can.Flow reactor is as carried sieve plate boiling chloridizing furnace, during using this reactor reaction, the carbon oxygen titanium valve of generation End will be sink to reactor bottom under gravity, periodically exclude and realize continuous prodution；Using hermetically sealed can such as nickel crucible During reaction, can be by raw material being charged in hermetically sealed can, temperature reaction, terminates heel row and removes tail gas to obtain required product.

The present invention prepares that carbon oxygen titanium is good with respect to carbothermic method uniformity, and because the present invention is gas phase reaction, its forming core is very Difficult a length of large particulate matter, therefore product is superfine and uniform, beneficial to follow-up processing and fabricating, is such as suitable as powder metallurgy, solvable The raw material of anode electrolysis uses.

Specific embodiment

Carbon oxygen titanium is prepared using the inventive method, because product only has a kind of solid matter of carbon oxygen titanium, its composition can pass through Chemical means measure its ti, c and o and just can be determined whether as product, wherein Ti content reference national standard gb/t4701.1-2009 It is measured；C measures with reference to jb/t6647-2011；O then adopts the o-3000 type pulsed infrared thermal conductivity that Nanogram Corp. provides Oxygen-nitrogen analyzer is measured.

The specific embodiment of form by the following examples, remakes further specifically to the above of the present invention Bright, illustrate but do not limit the present invention.

Embodiment one

The nickel crucible for φ 300 for the internal diameter is assembled, wherein sealing surface is sealed using polytetrafluoroethylene gasket, and Do water-cooled protection, after evacuation pretreatment, be passed through 160gco and 60gh₂Mixture, is warming up to 600 by 10 DEG C/min heating rate DEG C, then it is slowly introducing 1900g ticl₄, after insulation 1h, being passed through argon derives residual air (naoh mass fraction is to alkali liquor 10%) in, then directly carry out burn processing, when tail gas cannot burn, blowing out is cooled to room temperature, taking out weighing products is 580g, analyzing its result after testing is: 77.2%ti, 9.9%c and 12.9%o, meets tic_0.5o_0.5Carbon oxygen titanium composition ratio Example.

Embodiment two

The nickel crucible for φ 300 for the internal diameter is assembled, wherein sealing surface is sealed using polytetrafluoroethylene gasket, and Do water-cooled protection, after evacuation pretreatment, be passed through 180gco and 70gh₂Mixture, is warming up to 800 by 10 DEG C/min heating rate DEG C, then it is slowly introducing 1900g ticl₄, after insulation 1h, being passed through argon derives residual air to alkali liquor (koh mass fraction be 10%) In, then directly carry out burn processing, when tail gas cannot burn, blowing out is cooled to room temperature, taking-up weighing products are 611g, warp Testing and analyzing its result is: 77.0%ti, 9.7%c and 13.3%o, meets tic_0.5o_0.5Carbon oxygen titanium component ratio.

Embodiment three

It is passed through argon emptying 15min by 5l/min speed in internal diameter is for φ 150 boiling chloridizing furnace, then pass to temperature 500 DEG C of co and h₂Mixture (mol ratio is 1:4), and 500 DEG C of ticl₄Steam, wherein mixture flow rate control in 1l/min, ticl₄Gas flow controls in 0.5l/min, needs tail gas is processed, and method carries out 30min with embodiment two, reaction Afterwards, product is taken out in cooling is 502g, and analyzing its result after testing is 77.6%ti, 10.1%c and 12.3%o, meets tic_0.5o_0.5Carbon oxygen titanium component ratio.

Example IV

It is passed through argon emptying 15min by 5l/min speed in internal diameter is for φ 150 boiling chloridizing furnace, then pass to temperature 500 DEG C of co and h₂Mixture (mol ratio is 1:4), and 800 DEG C of ticl₄Steam, wherein mixture flow rate control in 1l/min, ticl₄Gas flow controls in 1l/min, needs tail gas is processed, and method, with embodiment two, is reacted after carrying out 30min, It is 315g that product is taken out in cooling, and analyzing its result after testing is 77.4%ti, 9.9%c and 12.7%o, meets tic_0.5o_0.5's Carbon oxygen titanium component ratio.

Above-described embodiment prepares that gained solid state powder is superfine and uniformity is good, meets the physics and chemistry such as carbon oxygen titanium conduction, hardness Can require, be adapted as powder metallurgy, the raw material of soluble anode electrolysis uses.

Claims (9)

1. carbon oxygen titanium preparation method it is characterised in that: comprise the following steps:

A, control temperature of reaction system at 400～800 DEG C, by gaseous ticl₄With co and h₂It is fully contacted reaction, ticl₄、co、 h₂It is calculated in molar ratio as 1:1.2～2:2.4～4；

B, collection form deposition gained solid content with solid, and this solid content is carbon oxygen titanium.

2. carbon oxygen titanium according to claim 1 preparation method it is characterised in that: reaction terminates rear tail gas and passes sequentially through alkali Liquid absorption is processed, and lights process, finally discharges.

3. carbon oxygen titanium according to claim 2 preparation method it is characterised in that: described alkali liquor be naoh aqueous solution, koh Aqueous solution.

4. the carbon oxygen titanium according to Claims 2 or 3 preparation method it is characterised in that: described alkali liquor mass fraction be 5- 20%.

5. carbon oxygen titanium according to claim 4 preparation method it is characterised in that: described alkali liquor mass fraction be 10%.

6. carbon oxygen titanium according to claim 1 preparation method it is characterised in that: anti-using flow reactor or hermetically sealed can Should.

7. carbon oxygen titanium according to claim 6 preparation method it is characterised in that: described flow reactor be fluidizing chlorination Stove.

8. carbon oxygen titanium according to claim 7 preparation method it is characterised in that: described boiling chloridizing furnace be band sieve plate boiling Rise chlorination furnace.

9. carbon oxygen titanium according to claim 6 preparation method it is characterised in that: described hermetically sealed can is nickel crucible.